Oximino phosphorus compounds

ABSTRACT

Compounds having the formula   IN WHICH X is oxygen or sulfur; Y is oxygen or sulfur; R is alkyl; R1 is alkyl; R2 is alkyl or alkoxy and R3 is (1) phenyl or (2) mono-, di- or tri-substituted phenyl wherein the substituent is (a) nitro, (b) cyano, (c) halogen, (d)   WHEREIN R4 is alkyl, (e) CF3, (f) SO2NHR5 wherein R5 is alkyl or (g) thiomethyl and their use as insecticides and acaricides are disclosed. Also, the intermediates for preparing the compounds and a method for preparing the intermediates are disclosed.

United States Patent 1 1 Gutman OXIMINO PHOSPl-IORUS COMPOUNDS [75] Inventor: Arnold D. Gutman, Berkeley, Calif.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn.

[22] Filed: Apr. 6, 1970 [2]] Appl. No.: 26,103

[52] US. Cl. 260/940; 260/543 P; 260/944;

260/968; 424/210; 424/211 [51] Int. Cl. C07F 9/165; AOlN 9/36 [58] Field of Search 260/940, 944

[56] References Cited UNITED STATES PATENTS 12/1957 Allen 260/944 X 10/1960 Diamond 260/944 X Primary ExaminerAnton l-l. Sutto Attorney, Agent, or FirmEdwin H. Baker [57] ABSTRACT Compounds having the formula July 29, 1975 in which X is oxygen or sulfur; Y is oxygen or sulfur; R is alkyl; R is alkyl; R is alkyl or alkoxy and R is (1) phenyl or (2) mono-, dior tri-substituted phenyl wherein the substituent is (a) nitro, (b) cyano, (c) hal- 8 6 Claims, N0 Drawings OXIMINO PHOSPHORUS COMROUNDS in which X is oxygen or sulfur; Y is oxygen or sulfur;

R is (1) alkyl having 1 to 8 carbon atoms, preferably branched chain or methyl, more preferably methyl and t-butyl;

R is alkyl having 1 to 4 carbon atoms, preferably methyl;

R is alkyl having l to 4 carbon atoms, preferably 1 to 2 carbon atoms; or alkoxy having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms;

R is (l) phenyl or (2) mono-, dior tri-substituted phenyl wherein the substituent is (a) nitro, (b) cyano, (c) halogen, preferably chlorine, (d)

wherein R is alkyl having 1 to 4 carbon atoms, preferably methyl, (e) CF (f) SO NHR wherein R is alkyl having 1 to 4 carbon atoms; or (g) thiomethyl, preferably mono substitution is in the meta or para positions and the substituent is a halogen, nitro, thiomethyl, CF- or cyano group, di substitution is meta and para or ortho and para and the substituents are both halogen groups and tri-substitution is in the 2,4,5 position and the substituents are all halogen, preferably chlorine. Optionally, such groups as alkyl having 1 to 4 carbon atoms or (h) alkoxy having 1 to 4 carbon atoms can also be substituted on the phenyl, preferably in the meta position.

The compounds of the present invention can be prepared according to the following reactions:

in which R, R, R R X and Y are as defined.

The process of this invention is represented by reaction 1(a) and gives the novel intermediatesof this invention. In other, words, the process is for preparing a compound having the formula in which R, R, R and X are as defined comprising rcacting a compound of the formula in which R and R are as defined with a compound of the formula to rin which R and X are as defined.

Preferably, reaction 1(a) is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used, the reaction still proceeds but yields are reduced. The reactants can be combined in any desired manner but preferably, the reaction is run in a solvent such as THF by first preparing the salt of the oxime reactant with an acid acceptor such as potassium t-butoxide at room temperature and then preferably slowly adding the dichloride reactant thereto, preferably in solution with a solvent, for example, THF, at a temperature below about 15C. for control. However, the oxime reactant'canbe used in place of the salt preferably in the presence of the acid acceptor. The resulting product is recovered and purified by standard procedure. For example, theresulting product can be recovered from the reaction mixture and purified from the reaction mixture by adding the mixture to a non-polar solvent such as benzene. The benzene mixture is then washed with water, dilute NaOH solution and then again by water. The benzene is evaporated after the water has been removed, for example, by treatment with anhydrous MgSO, to yield the purified product.

The novel intermediate compounds of this invention which are useful in preparing the insecticidal and acaricidal compounds of this invention, for example, by reaction l(b), heretofore described are those having the formula bly lQto 2 carbonatoms. These intermediate compounds can be prepared according to reaction 1(a) specifically described heretofore.

The reaction, reaction 1(1)). is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used. the reaction still proceeds but yields are reduced. The reactants can be combined in any manner. for example. the phosphoruscontaining reactant is slowly added to the phenol or triophenol reactant in a solvent such as THF. preferably with stirring. More preferably. an alkali metal salt of the phenol or thiophenol salt is used to reduce the chance of a violent reaction. The temperature of the reaction is not critical. however. generally better yields ane obtained by heating the reactants at reflux for a time sufficient to allow completion of the reaction. The resulting product can be recovered from the reaction mixture and purified by standard procedures. For example, the desired reaction product can be recovered from the reaction mixture by adding the mixture to a non-polar solvent such as benzene. The benzene mixture is then washed with water, dilute NaOH solution and then again by water. The benzene is evaporated after the water has been removed. for example. by treatment with anhydrous MgSO to yield the purified product. I

Preparation of the compounds of this invention, the intermediate compounds of this invention and the process of this invention for preparing said intermediate compounds are illustrated by the following examples:

' phonothionic dichloride is combined with 100 ml. of tetrahydrofuran in a 1 liter three-neck flask fitted with a stirrer. thermometer and dropping funnel. The solution is cooled in an ice bath and stirred. The oxime salt solution is added over a period of minutes at such a rate that the temperature does not exceed 15C. After the addition is complete, the resulting mixture is stirred at room temperature :for 1 hour. then poured into 400 ml. of benzene. The benzene mixture is washed with two 300 ml. portions of H 0, dried with anhydrous MgSO and evaporated under reduced pressure to yield 15.2 grams (76.2 percent of theory) of O- (acetoneoximino). ethyl. thiophosphonyl N,,- 1.5184. The compound is characterized by IR and NMR.

O-( Acetoneoximino ethyl-"( 4-nitrophenyl )thionophospho'nate. i i

7 grams (0.0503 moles) of 4-nitrophe'nol 'is combined with 2.1 grams (0.0503 moles) of caustic and mil. of water in a 500 ml. three-neck flask fitted with a stirchloride.

rer. thermometer and dropping funnel. The mixture is stirred and 10 grams (0.0503 moles) of O- (acetoneoximino). ethylthiophosphoryl chloride. obtained in Example 1. in 200 ml. of tetrahydrofuran is added over a period of 30 minutes. The resulting mixture is stirred and heated under reflux for 2 hours. cooled and poured into 400ml. of benzene. The benzcne mixture is washed with 200 ml. of H 0. 200 ml. dilute NaOH solution. followed by two 200 ml. portions of H 0. The benzene is dried with anhydrous MgSO, and evaporated to yield 10.9 grams (72.3% of theory) of the desired compound. O-(acetoneoximine). ethyl- (4-nitrophenyl)-thiophosphonate. m.p. 8287C. The compound is characterized by IR and NMR.

EXAMPLE lll O-(Acetoneoximino) O-ethyl thiophosphoryl chloride.

17.9 grams (0.1 moles) of ethyldichlorothiophosphate is combined with 20 ml. of tetrahydrofuran in a 250 ml. three-neck flask fitted with a stirrer. thermometer and dropping funnel. The solution is stirred and cooled to lOC. A solution of 9.5 grams (0.13 moles) of acetoneoxime, 4.0 grams (0.1 moles) of caustic, and 20 ml. of water is added to the stirring solution over a period of 30 minutes. The resulting mixture is stirred for 1 hour at 0C. and 30 mm at room temperature until the mixture becomes neutral to pH paper. The mixture is then poured into 300 ml. of Et O and is washed with two m1. portions of H 0. The Et O phase is dried with anhydrous MgSO and evaporated to yield 21.4 grams (99.9 percent of theory) of the desired compound. N,, 1.5037. The structure is characterized by IR and NMR.

EXAMPLE 1V O-(Acetoneoximino)-O-ethy|-O'(4-nitrophenyl) phosphorothioate.

10.0 grams (0.0465 moles) of O-(acetoneoximino), O-ethyl thiophosphoryl chloride obtained in Example 111 is reacted with 7 grams (0.0503 moles) of 4- nitrophenol and 2.1 grams (0.0503 moles) of caustic in the same manner as Example 11 to yield 12.6 grams (85.5 percent of theory) of the desired compound. N

- 1.5335. Compound is characterized by NMR and IR.

EXAMPLE V O-(Acetoneoximino) O-ethylphosphorochloridate.

In a 600 m1. beaker. 11.02 grams (0.1 moles) of potassium t-butoxide is combined with 300 m1. of tetrahydrofuran. The mixture is stirred in an ice bath and 7.3 grams (0.1 mole) of acetoneoxime is added over a period of 5 minutes. 16.3 grams (0.1 mole) of ethyldichlorophosphate is combined with 100 ml. of tetrahydrofuran in a 1-liter three-neck flask fitted with a dropping funnel. stirrer and thermometer. .The solution is stirred and cooled in an ice bath. The oxime salt is added over a period of 15 minutesvat such a rate that the temperature does not exceed 15C. After the addition is complete, the resulting mixture is stirred at room temperature for 1 hour. 400 ml. of benzene is added and the mixture is washed with two 300 ml. portions of water. The benzene phase is dried with anhydrous magnesium sulfate and evaporated under reduced pressure to yield 16.8 grams (84.3% of theory) of the desired product. N 1.4560. The structure is confirmed by NMR.

EXAMPLE V] O-(Acetoneoximino) O-ethyl-O-(4- nitrophenyl)phosphate.

grams (0.0503 moles) of O-(acetoneoximino) O- ethyl phosphorochloridate is combined with 300 m1. of tetrahydrofuran in a 500 ml. three-neck flask fitted with a stirrer, dropping funnel, thermometer and reflux condenser. The solution is stirred and cooled to 5C. in an ice bath. 7.0 grams (0.05 moles) of 4-nitrophenol, 2.1 grams (0.0503 moles) of caustic and 25 ml. of water are combined in a 50 ml. beaker. The resulting salt solution is added to the chloridate at such a rate that the temperature does not exceed C. The resulting mixture is stirred at room temperature for 1 hour and is heated under reflux for 1 hour. The mixture is cooled to room temperature and 400 ml. of benzene is added. The mixture is washed in turn with 200 ml. of water, 200 ml. dilute caustic and two 200 ml. portions of water. The benzene phase is dried with anhydrous magnesium sulfate and evaporated under reduce of pressure to yield 10.5 grams (69.5%. of theory) of the desired compound. N 1.5280. The structure is confirmed by the infrared spectrum.

EXAMPLE VII g 6 O(Acetoneoximino) ethyl-S-phenylphosphonodithioate. -S-phenylphosphonodithioate.

5.5 grams (0.0505 moles) of thiophenol is combined with 2.1 grams (0.0503 moles) of caustic and 25 ml. of water in a 500 ml. three-neck flask fitted with a stirrer. thermometer and dropping funnel. The mixture is stirred and 10 grams (0.0503 moles) of O- (acctoneoximino) ethylthiophosphoryl chloride. obtained in Example I, in 200 ml. tetrahydrofuran is added over a period of 30 minutes. The resulting mixture is stirred and heated under reflux for 2 hours. cooled and poured into 400 ml. of benzene. The benzene mixture is washed with 200 ml. of water. 200 ml. of dilute caustic solution. followed by two 200 ml. portions of water. The benzene phase is dried with anhydrous MgSO. and evaporated under reduced pressure to yield 10.8 grams (79.2% of theory) of the desired compound. N 1.5830. The compound is characterized by IR.

EXAMPLE Vlll O-(Acetoneoximino) O-ethyl-S-phenylphosphorothioate.

5.5 grams (0.0505 moles) of thiophenol is combined with 2.1 grams (0.0503 moles) of caustic and 25 ml. of water in a 500 ml. three-neck flask fitted with a stirrer. thermometer. and dropping funnel. The mixture is stirred and 10 grams (0.0503 moles of O- (acetoneoximino) O-ethylphosphorochloridate, obtained in Example V, in 200 ml. of tetrahydrofuran is added over a period of 30 minutes. The resulting mixture is stirred and heated under reflux for 2 hours. cooled and poured into 400 ml. of benzene. The benzene mixture is washed with 200 ml. of water, 200 ml. of dilute caustic solution, followed by two 200 ml. portions of water. The benzene phase is dried with anhydrous MgSO and evaporated under reduced pressure to yield 6.5 grams (50.5 percent of theory) of the desired compound. N f 1.5642. The compound is characterized by IR and NMR.

The following is a table of certain selected com- (11 '7 g pounds that are preparable according to the procedure q vw'l/ I c. .o described hereto. Compound numbers are assigned to C} each compound and are used throughout the remain- J z 3 der of the application.

TABLE I Com- 0 pound I m.p. C Number R R R2 X Y R" or N,,"

1" cH CH. H. s 0 440 8241? CH 2 CH3 CH3 C H S O 02 71-74 3 0H,, CH. C H s o Q-cu 74-76 4" CH. CH. c s s 1.5830

TABLE] CONTINUED CommpT d I bl rlber R R I R2 X Y R3 or N,;

711 cH,, -,c CH3 CH, 5 0 0 1.5100

79 c11,, .-.c C11,, 7e11,, s o I .Q-m 1.521s

80 (c11 ,c C11, c1-1, s 0 c1 1.525s

s1 c1-1 -,).,c 1:11 C11,, s s 1.5642

82" ca, can 00 11,, 0 s 0 1.5642

(F3 83 CH" CH, cat, s 0 1.5005

84 CH;, CH, H, s o 15x94 85 CH, C 0.11,, s o 1.5240

9' 86 CH, CH, c 111., s 0 SO2NH l.548() "Compound No. I prepared in Example ll Compound No. 4 prepared in Example VII "Compound No. l3 prepared in Example VI "Compound No. prepared in Example IV "Compound No. 82 prepared in Example VIII The following tests illustrate utility of the compounds as insecticides and acaricides.

INSECTICIDAL EVALUATION TESTS The following insect species were used in evaluation tests for insecticidal activity:

1. Housefly (HF) Musca domestica (Linn.)

2. German Roach (GR) Blatella germanica (Linn.)

3. Salt-Marsh Caterpillar (SMC) Estigmene acrea (Drury) 4. Lygus Bug (LB) Lygus hesperus (Knight) 5. Bean Aphid (BA) Aphis fabae (Scop.)

The l-lousefly (HF) was used in evaluation tests of selected compounds as insecticides by the following procedure. A stock solution containing 100 ug/ml of the toxicant in an appropriate solvent was prepared. Aliquots of this solution were combined with 1 milliliter of an acetone-peanut oil solution in an aluminum dish and allowed to dry. The aliquots were there to achieve desired toxicant concentration ranging from 100 ug per dish to that at which 50 percent mortality was attained. The dishes were placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female houseflies, 3 to 5 days old, were introduced into the cage and the percent mortality was recorded after 48 hours. The

ranged from 0.1 percent downward to that at which 50 percent mortality was obtained. Each of the aqueous suspensions of the candidate compounds was sprayed onto the insects through the cloth netting by means of a hand-spray gun. Percent mortality in each case was recorded after 72 hours, and the LD-SO values expressed as percent of toxicant in the aqueous spray were recorded. These values are reported under the column GR" in Table II.

For testing the Salt Marsh Caterpillar, test solutions were prepared in an identical manner and at concentrations the same as for the German Cockroach above. Sections of bitter dock (Rumex obruszfolusfieaves, l 1.5 inches in length were immersed in the test solutions for 10 to 15 seconds and placed on a wire screen to dry. The dried leaf was placed on a moistened piece of filter paper in a Petri dish and infested with 5 3rd Iristar larvae. Mortality of the larvae was recorded after 72 hours and the LD-SO values are expressed as percent active ingredient in the aqueous suspension.

The Lygus Bug (LB) Lygus hesperus was tested similarly as the German Cockroach. The caged insects were sprayed with the candidate compounds at concentrations ranging from 0.05% downward to that at which 50 percent mortality was obtained. After twenty-four and 72 hours, counts were made to determine living and dead insects. The LD-SO (percent) values were calculated. These values are reported under the column LB in Table ll.

The insect species black bean aphid (BA) Aphisfabae (Scop.) was also employed in the test for insecticidal activity. Young nasturtium (Tropaeolum sp.) plants, approximately 2 to 3 inches tall, were used as the host plants for the bean aphid. The host plant was infested with approximately 50 75 of the aphids. The test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221", an

emulsifying agent. The solution was applied as a spray to the infested plants. Concentrations ranged from 0.05 percent downward until an LD; value was achieved. These results are given in Table II under the column SYSTEMIC EVALUATION TEST This test evaluates the root absorption and upward translocation of the candidate systemic compound. The two-spotted mite (ZSM Tetranyclms urlicae (Koch) 5 and the Bean Aphid (BA). Aphis fabue (Scop.) were employed in the test for systemic activity.

Young pinto bean plants in the primary leaf stage ACAR CID EVALUATION TEST were used as host plants for the two-spotted mite. The pinto bean plants were placed in bottles containing 200 l ml. of the test solution and held in place with cotton The twosponed e (25M), Tetra/{861185 mule plugs. Only the roots were immersed. The test solutions (Koehlwas employed In tests for mmeldes' Young were prepared by dissolving the compounds to be P been plants or bean Plants (Phaswlus 317') tested in a suitable solvent, usually acetone, and then the pnmery leaf stage were e as the e plants' The diluting with distilled water. The final acetone concenyoung P been Plants were Infested l about 9 tration never exceeded about 1 percent. The toxicants mites of Venous dges- Dlsperslons of eandleate mater" were initially tested at a concentration of parts per als were P p y dlssolvmg gram 10 ml of million (p.p.m.). Immediately after the host plant was Sultable Solvemusually acetone Allquots of the toxl placed in the test solution it was infested with the test 011m Solutlons were Suspended Water eonmmmg species. Mortalities were determined after 7 days. O-OOZ Percent SPOntO 221R, P y y y ether 20 Young nasturtium plants were used as the host plants sorbitan mono aurate, an emulslfymg agent, e for the bean aphid. The host plants were transplanted amount of water being sufficient to give concentrations into one pound of soil that had been treated with the of active ingredient ranging m 0.05 Percent 10 that candidate compound. Immediately after planting in the at which 50 percent mortality as ta d- The 6 treated soil the plants were infested with the aphids. suspensions were then sprayed on the infested plants to 25 Concentrations of toxicant in the soil ranged from 10 the point of run off. After seven days, mortalities of p.p.m. per pound of soil downward until an LD-50 post-embryonic and ovicidal forms were determined. value was obtained. Mortality was recorded after 72 The percentage of kill was determined by comparison hours. with control plants which had not been sprayed with The percentage of kill of each test species was deterthe candidate compounds. The LD-5O values were cal- 30 mined by comparison with control plants placed in disculated using well-known procedures. These values are tilled water or untreated soil. The LD5O values were reported under the columns ZSM-PE" and ZSM- calculated. These systemic test results are reported in Eggs" in Table II. Table II under the columns BA-sys and ZSM-sys.

' i TABLE II LD VALUES Two-Spotted Mites Compound HF GR LB SM BA BASYS PE EGGS SYS Number ug "/r "/0 p.p.m. p.p.m.

TABLE 11 CONTINUED 15" Two-Spotted Mites Compound HF GR LB SMC BA BA-SYS PE EGGS SYS Number ug 7n ppm. 71/ p.p.m.

46 30 .l .008 .1 .003 8.0 .01 .03 10 47 10 .05 .005 .l .005 10.0 .003 .01 10 48 24 .03 .008 .01 .005 3 .0 .008 .03 8 49 7 .08 .008 .05 .003 10.0 .003 .05 10 50 15 .1 .01 .005 .001 10.0 .005 .03 10 51 30 .1 .05 .03 .003 10.0 .003 .05 10 52 14 .03 .03 .03 .003 10.0 .003 .05 10 53 8 .03 .003 .003 .001 10.0 .001 .003 10 54 3 .005 .003 .003 .001 10.0 .001 .003 10 55 30 .1 .01 .03 .003 10.0 .003 .03 10 56 45 .1 .03 .03 .008 100 .01 .03 10 57 90 .1 .05 .1 .03 10.0 .03 .05 10 58 15 .08 .03 .05 .03 100 .001 .03 10 59 30 .08 .01 .03 .003 10.0 .03 .05 10 60 7 .03 .003 .03 .003 10.0 .001 .03 10 61 3 .03 .001 .05 .003 5.0 .003 .03 3 62 70 .1 .05 .1 .03 10.0 .008 .05 10 63 30 .1 .05 .1 .03 10.0 .05 .05 10 64 12 .1 .05 .1 .003 10.0 .005 .05 10 65 30 .l .03 .1 .005 10.0 .03 .05 10 66 60 .1 .05 .1 .05 10.0 .05 .05 10 67 30 .08 .01 .01 .001 10.() .03 .03 10 68 40 .1 .05 .01 .003 1 0.0 .05 .05 10 69 12 .l .005 .01 .0003 l0.0 .03 .05 10 70 8 .03 .005 ()1 .0008 10.0 .008 .05 10 71 30 .1 .005 .03 .03 l0.0 .05 .05

As those in the art are well aware, various techniques are available for incorporating the active component or toxicant in suitable pesticidal compositions. Thus, the pesticidal compositions can be conveniently prepared in the form of liquids or solids, the latter preferably as homogeneous free-flowing dusts commonly formulated by admixing the active component with finely divided solids or carriers as exemplified by talc, natural clays, diatomaceous earth, various flours such as walnut shell, wheat, soya bean, cottonseed and so forth.

Liquid compositions are also useful and normally comprise a dispersion of the toxicant in a liquid media, although it may be convenient to dissolve the toxicant directly in a solvent such as kerosene, fuel oil, xylene, alkylated naphthalenes or the like and use such organic solutions directly. However, the more common procedure is to employ dispersions of the toxicant in an aqueous media and such compositions may be produced by forming a concentrated solution of the toxicant in a suitable organic solvent followed by dispersion in water, usually with the aid of surface active agents. The latter, which may be the anionic, cationic, or nonionic types, are exemplified by sodium stearate, potassium oleate and other alkaline metal soaps and detergents such as sodium lauryl sulfate, sodium naphthalene sulfonate, sodium alkyl naphthalene, sulfonate, methyl cellulose, fatty alcohol ethers, polyglycol fatty acid esters and other polyoxyethylene surface active agents. The proportion of these agents commonly comprises 1 15 percent by weight of the pesticidal compositions although the proportion is not critical and may be varied to suit any particular situation.

I claim:

l. A compound having the formula R x Y-R3 in which X is sulfur, Y is oxygen, R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is 2,4,5-trichlorophenyl.

4. The compound of claim 3 in which R is methyl, R is methyl and R is ethyl.

5. A compound having the formula in which X is sulfur, Y is sulfur, R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is phenyl.

6. The compound of claim 5 in which R is methyl, R is methyl and R is ethyl. 

1. A COMPOUND HAVING THE FORMULA
 2. The compound of claim 1 in which R is methyl, R1 is methyl and R2 is ethyl.
 3. A COMPOUND HAVING THE FORMULA
 4. The compound of claim 3 in which R is methyl, R1 is methyl and R2 is ethyl.
 5. A COMPOUND HAVING THE FORMULA
 6. The compound of claim 5 in which R is methyl, R1 is methyl and R2 is ethyl. 